U.S. patent application number 16/101257 was filed with the patent office on 2018-12-20 for high charge density metallophosphate molecular sieves.
The applicant listed for this patent is UOP LLC. Invention is credited to Suk Bong Hong, Lisa M. Knight, Junghwan Lee, Gregory J. Lewis, Jaime G. Moscoso, Christopher P. Nicholas, Seungwan Seo.
Application Number | 20180361368 16/101257 |
Document ID | / |
Family ID | 60412525 |
Filed Date | 2018-12-20 |
United States Patent
Application |
20180361368 |
Kind Code |
A1 |
Lewis; Gregory J. ; et
al. |
December 20, 2018 |
HIGH CHARGE DENSITY METALLOPHOSPHATE MOLECULAR SIEVES
Abstract
A family of highly charged crystalline microporous
metallophosphate molecular sieves designated PST-17 has been
synthesized. These metallophosphates are represented by the
empirical formula of:
R.sup.p+.sub.rA.sub.m.sup.+M.sub.xE.sub.yPO.sub.z where A is an
alkali metal such as potassium, R is a quaternary ammonium cation
such as ethyltrimethylammonium, M is a divalent metal such as zinc
and E is a trivalent framework element such as aluminum or gallium.
The PST-17 family of molecular sieves are stabilized by
combinations of alkali and organoammonium cations, enabling unique
metalloalumino(gallo)phosphate compositions and exhibit the BPH
topology. The PST-17 family of molecular sieves has catalytic
properties for carrying out various hydrocarbon conversion
processes and separation properties for separating at least one
component.
Inventors: |
Lewis; Gregory J.; (Santa
Cruz, CA) ; Nicholas; Christopher P.; (Evanston,
IL) ; Knight; Lisa M.; (Chicago, IL) ;
Moscoso; Jaime G.; (Mount Prospect, IL) ; Seo;
Seungwan; (Gyeongsangnam-do, KR) ; Hong; Suk
Bong; (Jikok-Dong, KR) ; Lee; Junghwan;
(Uijeongbu, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
UOP LLC |
Des Plaines |
IL |
US |
|
|
Family ID: |
60412525 |
Appl. No.: |
16/101257 |
Filed: |
August 10, 2018 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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PCT/US2017/033749 |
May 22, 2017 |
|
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16101257 |
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62341172 |
May 25, 2016 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10G 45/04 20130101;
C10G 3/48 20130101; B01J 31/02 20130101; B01J 29/061 20130101; C10G
50/00 20130101; C10G 29/205 20130101; B01J 37/04 20130101; C10G
47/12 20130101; Y02P 30/20 20151101; C10G 45/60 20130101; C10G
35/065 20130101; C01B 37/08 20130101; C01B 39/54 20130101; B01J
29/84 20130101; B01J 37/0018 20130101; C10G 11/04 20130101 |
International
Class: |
B01J 29/84 20060101
B01J029/84; C01B 39/54 20060101 C01B039/54; B01J 37/04 20060101
B01J037/04; B01J 37/00 20060101 B01J037/00 |
Claims
1. A microporous crystalline metallophosphate material having a
three-dimensional framework of [M.sup.2+O.sub.4/2].sup.2-,
[EO.sub.4/2].sup.- and [PO.sub.4/2].sup.+ tetrahedral units and an
empirical composition in the as synthesized form and anhydrous
basis expressed by an empirical formula of:
R.sup.p+.sub.rA.sup.+.sub.mM.sup.2+.sub.xE.sub.yPO.sub.z where R is
at least one quaternary ammonium cation selected from the group
consisting of ethyltrimethylammonium (ETMA.sup.+),
diethyldimethylammonium (DEDMA.sup.+), hexamethonium (HM.sup.2+),
choline [Me.sub.3NCH.sub.2CH.sub.2OH].sup.+,
trimethylpropylammonium, trimethylbutylammonium,
trimethylisopropylammonium, tetramethylammonium (TMA.sup.+),
tetraethylammonium (TEA.sup.+), tetrapropylammonium (TPA.sup.+) and
mixtures thereof, "r" is the mole ratio of R to P and has a value
of about 0.1 to about 1.0, "p" is the weighted average valence of R
and varies from 1 to 2, A is an alkali metal selected from the
group consisting of Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+ and
Cs.sup.+ and mixtures thereof, "m" is the mole ratio of A to P and
varies from 0.1 to 1.0, M is a divalent element selected from the
group of Zn, Mg, Co, Mn and mixtures thereof, "x" is the mole ratio
of M to P and varies from 0.2 to about 0.9, E is a trivalent
element selected from the group consisting of aluminum and gallium
and mixtures thereof, "y" is the mole ratio of E to P and varies
from 0.1 to about 0.8 and "z" is the mole ratio of O to P and has a
value determined by the equation: z=(m+p r+2 x+3 y+5)/2 and is
characterized in that it has the x-ray diffraction pattern having
at least the d-spacings and intensities set forth in Table A:
TABLE-US-00010 TABLE A 2.THETA. d(.ANG.) I/I.sub.0 % 6.90-6.64
12.80-13.31 s-vs 7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w
13.68-13.30 6.47-6.65 w-m 14.95-14.63 5.92-6.05 w 15.64-15.32
5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m
21.5-20.98 4.13-4.23 w-m 24.03-23.58 3.70-3.77 w 24.37-23.97
3.65-3.71 w-s 26.75-26.386 3.33-3.375 w-m 27.51-27.04 3.24-3.295
w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.13 3.12-3.17 w-m
28.87-28.45 3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m
30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.03
2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m
35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w 38.44-37.851
2.34-2.375 w 40.04-39.528 2.25-2.278 w 41.19-40.567 2.19-2.222 w
43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w
2. The metallophosphate material of claim 1 where A is
potassium.
3. The metallophosphate material of claim 1 where E is aluminum.
The metallophosphate material of claim 1 where R is
ethyltrimethylammonium cation, ETMA.sup.+.
5. The metallophosphate material of claim 1 where R is the
diethyldimethylammonium cation, DEDMA.sup.+.
6. The metallophosphate material of claim 1 where R is the
trimethylisopropylammonium cation.
7. A crystalline modified form of the crystalline microporous
metallophosphate of claim 1, comprising a three-dimensional
framework of [M.sup.2+O.sub.4/2].sup.2-, [EO.sub.4/2].sup.- and
[PO.sub.4/2].sup.+ tetrahedral units and derived by modifying the
crystalline microporous metallophosphate of claim 1, the
modifications comprising calcination, ammonia calcinations,
ion-exchange, steaming, various acid extractions, ammonium
hexafluorosilicate treatment, or any combination thereof.
8. A method for preparing a microporous crystalline
metallophosphate material having a three-dimensional framework of
[M.sup.2+O.sub.4/2].sup.2-, [EO.sub.4/2].sup.- and
[PO.sub.4/2].sup.+ tetrahedral units and an empirical composition
in the as synthesized form and anhydrous basis expressed by an
empirical formula of:
R.sup.p+.sub.rA.sup.+.sub.mM.sup.2+.sub.xE.sub.yPO.sub.z where R is
at least one quaternary ammonium cation selected from the group
consisting of ethyltrimethylammonium (ETMA.sup.+),
diethyldimethylammonium (DEDMA.sup.+), hexamethonium (HM.sup.2+),
choline [Me.sub.3NCH.sub.2CH.sub.2OH].sup.+,
trimethylpropylammonium, trimethylbutylammonium,
trimethylisopropylammonium, tetramethylammonium (TMA.sup.+),
tetraethylammonium (TEA.sup.+), tetrapropylammonium (TPA.sup.+) and
mixtures thereof, "r" is the mole ratio of R to P and has a value
of about 0.1 to about 1.0, "p" is the weighted average valence of R
and varies from 1 to 2, A is an alkali metal selected from the
group consisting of Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+ and
Cs.sup.+ and mixtures thereof, "m" is the mole ratio of A to P and
varies from 0.1 to 1.0, M is a divalent element selected from the
group of Zn, Mg, Co, Mn and mixtures thereof, "x" is the mole ratio
of M to P and varies from 0.2 to about 0.9, E is a trivalent
element selected from the group consisting of aluminum and gallium
and mixtures thereof, "y" is the mole ratio of E to P and varies
from 0.1 to about 0.8 and "z" is the mole ratio of O to P and has a
value determined by the equation: z=(m+p r+2 x+3 y+5)/2 and is
characterized in that it has the x-ray diffraction pattern having
at least the d-spacings and intensities set forth in Table A:
TABLE-US-00011 TABLE A 2.THETA. d(.ANG.) I/I.sub.0 % 6.90-6.64
12.80-13.31 s-vs 7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w
13.68-13.30 6.47-6.65 w-m 14.95-14.63 5.92-6.05 w 15.64-15.32
5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m
21.5-20.98 4.13-4.23 w-m 24.03-23.58 3.70-3.77 w 24.37-23.97
3.65-3.71 w-s 26.75-26.386 3.33-3.375 w-m 27.51-27.04 3.24-3.295
w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.13 3.12-3.17 w-m
28.87-28.45 3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m
30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.03
2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m
35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w 38.44-37.851
2.34-2.375 w 40.04-39.528 2.25-2.278 w 41.19-40.567 2.19-2.222 w
43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w
the process comprising forming a reaction mixture containing
reactive sources of R, A, E, M and P, and heating the reaction
mixture at a temperature of about 60.degree. C. to about
200.degree. C. for a time sufficient to form the metallophosphate
molecular sieve, the reaction mixture having a composition
expressed in terms of mole ratios of the oxides of:
aR.sub.2/pO:bA.sub.2O:cMO:E.sub.2O.sub.3:dP.sub.2O.sub.5:eH.sub.2O
where "a" has a value of about 2.1 to about 100, "b" has a value of
about 0.1 to about 8.0, "c" has a value of about 0.25 to about 8,
"d" has a value of about 1.69 to about 25, and "e" has a value from
30 to 5000.
9. The method of claim 8 where the initial reaction mixture is a
clear solution before digestion.
10. The method of claim 8 where A is selected from the group
consisting of Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+ and Cs.sup.+
and mixtures thereof and the source of A is selected from the group
consisting of halide salts, nitrate salts, acetate salts, sulfate
salts, hydroxide salts and mixtures thereof.
11. The method of claim 8 where M is selected from the group
consisting of Zn.sup.2+, Mn.sup.2+, Co.sup.2+ and Mg.sup.2+ and
mixtures thereof and where the source of M is selected from the
group consisting of halide salts, nitrate salts, acetate salts,
sulfate salts and mixtures thereof.
12. The method of claim 8 where the source of E is selected from
the group consisting of aluminum isopropoxide, aluminum
sec-butoxide, precipitated alumina, Al(OH).sub.3, alkali aluminate
salts, aluminum metal, aluminum halide salts, aluminum sulfate
salts, aluminum nitrate salts, precipitated gallium oxyhydroxide,
gallium nitrate, gallium sulfate and mixtures thereof.
13. The method of claim 8 where the reaction mixture is reacted at
a temperature of about 125.degree. C. to about 185.degree. C. for a
time of about 1 day to about 14 days.
14. The method of claim 8 where R is ethyltrimethylammonium,
ETMA.sup.+.
15. The method of claim 8 where R is diethyldimethylammonium,
DEDMA.sup.+.
16. The method of claim 8 further comprising adding PST-17 seeds to
the reaction mixture.
17. A hydrocarbon conversion process comprising contacting a
hydrocarbon stream with a catalyst at hydrocarbon conversion
conditions to generate at least one converted product, wherein the
catalyst is selected from the group consisting of a crystalline
microporous PST-17 material, a modified crystalline microporous
PST-17 material and mixtures thereof, where PST-17 is a crystalline
microporous metallophosphate having a three-dimensional framework
of [M.sup.2+O.sub.4/2].sup.2-, [EO.sub.4/2].sup.- and
[PO.sub.4/2].sup.+ tetrahedral units and an empirical composition
in the as synthesized form and anhydrous basis expressed by an
empirical formula of:
R.sup.p+.sub.rA.sup.+.sub.mM.sup.2+.sub.xE.sub.yPO.sub.z where R is
at least one quaternary ammonium cation selected from the group
consisting of ethyltrimethylammonium (ETMA.sup.+),
diethyldimethylammonium (DEDMA.sup.+), hexamethonium (HM.sup.2'),
choline [Me.sub.3NCH.sub.2CH.sub.2OH].sup.+,
trimethylpropylammonium, trimethylbutylammonium,
trimethylisopropylammonium, tetramethylammonium (TMA.sup.+),
tetraethylammonium (TEA.sup.+), tetrapropylammonium (TPA.sup.+) and
mixtures thereof, "r" is the mole ratio of R to P and has a value
of about 0.1 to about 1.0, "p" is the weighted average valence of R
and varies from 1 to 2, A is an alkali metal such as Li.sup.+,
Na.sup.+, K.sup.+, Rb.sup.+ and Cs.sup.+ and mixtures thereof, "m"
is the mole ratio of A to P and varies from 0.1 to 1.0, M is a
divalent element selected from the group of Zn, Mg, Co, Mn and
mixtures thereof, "x" is the mole ratio of M to P and varies from
0.2 to about 0.9, E is a trivalent element selected from the group
consisting of aluminum and gallium and mixtures thereof, "y" is the
mole ratio of E to P and varies from 0.1 to about 0.8 and "z" is
the mole ratio of O to P and has a value determined by the
equation: z=(m+p r+2 x+3 y+5)/2 and is characterized in that it has
the x-ray diffraction pattern having at least the d-spacings and
intensities set forth in Table A: TABLE-US-00012 TABLE A 2.THETA.
d(.ANG.) I/I.sub.0 % 6.90-6.64 12.80-13.31 s-vs 7.76-7.47
11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w 13.68-13.30 6.47-6.65 w-m
14.95-14.63 5.92-6.05 w 15.64-15.32 5.66-5.78 w-m 19.03-18.67
4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m 21.5-20.98 4.13-4.23 w-m
24.03-23.58 3.70-3.77 w 24.37-23.97 3.65-3.71 w-s 26.75-26.386
3.33-3.375 w-m 27.51-27.04 3.24-3.295 w-m 27.725-27.292 3.215-3.265
w-m 28.59-28.13 3.12-3.17 w-m 28.87-28.45 3.09-3.135 w-m
30.012-29.505 2.975-3.025 w-m 30.38-30.06 2.94-2.97 w-m 30.92-30.38
2.89-2.94 w-m 31.59-31.03 2.83-2.88 w 33.67-33.15 2.66-2.70 w-m
34.20-33.67 2.62-2.66 w-m 35.45-34.88 2.53-2.57 w-m 36.81-36.34
2.44-2.47 w 38.44-37.851 2.34-2.375 w 40.04-39.528 2.25-2.278 w
41.19-40.567 2.19-2.222 w 43.849-43.167 2.063-2.094 w 49.932-49.326
1.825-1.846 w
and the modified crystalline microporous PST-17 consists of a
three-dimensional framework of [M.sup.2+O.sub.4/2].sup.2-,
[EO.sub.4/2].sup.- and [PO.sub.4/2].sup.+ tetrahedral units derived
from PST-17 via the modification processes of calcination, ammonia
calcinations, ion-exchange, steaming, various acid extractions,
ammonium hexafluorosilicate treatment, or any combination
thereof.
18. The process of claim 17 wherein the hydrocarbon conversion
process is selected from the group consisting of cracking,
hydrocracking, alkylation, isomerization, polymerization,
reforming, hydrogenation, dehydrogenation, transalkylation,
dealkylation, hydration, dehydration, hydrotreating, hydrofining,
hydrodenitrogenation, hydrodesulfurization, methanol to olefins,
methanation, syngas shift process, olefin dimerization,
oligomerization, dewaxing, and combinations thereof
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of copending
International Application No. PCT/US2017/033749 filed May 22, 2017,
which application claims priority from U.S. Provisional Application
No. 62/341,172 filed May 25, 2016, now expired, the contents of
which cited applications are hereby incorporated by reference in
their entirety.
FIELD OF THE INVENTION
[0002] This invention relates to a family of charged
metallophosphate-based molecular sieves designated PST-17. They are
represented by the empirical formula of:
R.sup.p+.sub.rA.sup.+.sub.mM.sup.2+.sub.xE.sub.yPO.sub.z
where A is an alkali metal such as potassium, R is at least one
quaternary organoammonium cation such as ethyltrimethylammonium, M
is a divalent metal such as zinc and E is a trivalent framework
element such as aluminum or gallium. The PST-17 family of materials
has the BPH topology.
BACKGROUND OF THE INVENTION
[0003] Zeolites are crystalline aluminosilicate compositions which
are microporous and which are formed from corner sharing
[AlO.sub.4/2].sup.- and SiO.sub.4/2 tetrahedra. Numerous zeolites,
both naturally occurring and synthetically prepared are used in
various industrial processes. Synthetic zeolites are prepared via
hydrothermal synthesis employing suitable sources of Si, Al and
structure directing agents (SDAs) such as alkali metals, alkaline
earth metals, amines, or organoammonium cations. The structure
directing agents reside in the pores of the zeolite and are largely
responsible for the particular structure that is ultimately formed.
These species balance the framework charge associated with aluminum
and can also serve as space fillers. Zeolites are characterized by
having pore openings of uniform dimensions, having a significant
ion exchange capacity, and being capable of reversibly desorbing an
adsorbed phase which is dispersed throughout the internal voids of
the crystal without significantly displacing any atoms which make
up the permanent zeolite crystal structure. Zeolites can be used as
catalysts for hydrocarbon conversion reactions, which can take
place on outside surfaces of the zeolite as well as on internal
surfaces within the pores of the zeolite.
[0004] In 1982, Wilson et al. developed aluminophosphate molecular
sieves, the so-called AlPOs, which are microporous materials that
have many of the same properties of zeolites, but are silica free,
composed of [AlO.sub.4/2].sup.- and [PO.sub.4/2].sup.+ tetrahedra
(see U.S. Pat. No. 4,319,440). Subsequently, charge was introduced
to the neutral aluminophosphate frameworks via the substitution of
SiO.sub.4/2 tetrahedra for [PO.sub.4/2].sup.+ tetrahedra to produce
the SAPO molecular sieves (see U.S. Pat. No. 4,440,871). Another
way to introduce framework charge to neutral aluminophosphates is
to substitute [M.sup.2+O.sub.4/2].sup.2- tetrahedra for
[AlO.sub.4/2].sup.- tetrahedra, which yield the MeAPO molecular
sieves (see U.S. Pat. No. 4,567,029). It is furthermore possible to
introduce framework charge on AlPO-based molecular sieves via the
introduction both of SiO.sub.4/2 and [M.sup.2+O.sub.4/2].sup.2-
tetrahedra to the framework, giving MeAPSO molecular sieves (see
U.S. Pat. No. 4,973,785).
[0005] In the early 1990's, high charge density molecular sieves,
similar to the MeAPOs but without the Al, were developed by Bedard
(see U.S. Pat. No. 5,126,120) and Gier (see U.S. Pat. No.
5,152,972). These metal phosphates (sometimes arsenates, vanadates)
were based on M.sup.2+ (M.dbd.Zn, Co), the general formula of
which, in terms of the T-atoms, T.sup.2+-T.sup.5+, was
approximately Al.sup.+T.sup.2+T.sup.5+O.sub.4, having framework
charge densities similar to Si/Al=1 zeolites and were charge
balanced by alkali cations, A.sup.+, in the pores. Later attempts
to prepare metallophosphates of similar compositions but with
organic SDAs led to porous, but interrupted structures, i.e., the
structures contained terminal P--O--H and Zn--N bonds (see J.
MATER. CHEM., 1992, 2(11), 1127-1134). Attempts at Al substitution
in a zincophosphate network was carried out in the presence of both
alkali and organoammonium agents, specifically the most highly
charged organoammonium species, tetramethylammonium, but because of
the high framework charge density, only the alkali made it into the
pores to balance framework charge (see U.S. Pat. No. 5,302,362).
Similarly, in a high charge density zincophosphate system that
yielded the zinc phosphate analog of zeolite X, the synthesis in
the presence of Na.sup.+ and TMA.sup.+ yielded a product that
contained considerably less TMA.sup.+ than Na.sup.+ (see CHEM.
MATER., 1991, 3, 27-29).
[0006] To bridge the rather large charge density gap between the
MeAPOs of U.S. Pat. No. 4,567,029 and the aforementioned
alkali-stabilized Me.sup.2+-phosphates of Bedard and Gier, Stucky's
group developed a synthesis route using amines, often diamines in
ethylene glycol-based reaction mixtures. They were able to make
high charge density, small pore MeAPOs in which the concentrations
of Co.sup.2+ and Al.sup.3+ in R(Co.sub.xAl.sub.1-x)PO.sub.4 were
varied such that 0.33.ltoreq.x.ltoreq.0.9 in the so-called ACP
series of materials, the aluminum cobalt phosphates (see NATURE,
1997, 388, 735). Continuing with this synthesis methodology
utilizing ethylene glycol solvent and matching the amines to
framework charge densities for R(M.sup.2+.sub.xAl.sub.1-x)PO.sub.4,
such that 0.4.ltoreq.x.ltoreq.0.5, (M.sup.2++Mg.sup.2+, Mn.sup.2+,
Zn.sup.2+, Co.sup.2+) the large pore materials UCSB-6, -8 and -10
were isolated (see SCIENCE, 1997, 278, 2080). Crystal dimensions
isolated from that work were often on the order of hundreds of
microns. Similarly, this approach also yielded MeAPO analogs of
zeolite rho of the composition where
RM.sup.2+.sub.0.5Al.sub.0.5PO.sub.4, where R=N,
N'-diisopropyl-1,3-propanediamine, M.sup.2+=Mg.sup.2+, Co.sup.2+
and Mn.sup.2+. The reliance of this synthesis approach on an
ethylene glycol solvent does not lend itself well to industrial
scale, from both a safety and environmental point of view. While
several others embraced Stucky's approach, there has been little
activity in this intermediate charge density region, where
0.2.ltoreq.x.ltoreq.0.9 for the
[M.sup.2+.sub.xAl.sub.1-xPO.sub.4].sup.x- compositions.
[0007] Pursuing aqueous chemistry, Wright et al. used highly
charged triquaternary ammonium SDAs to make new MeAPO materials
(see CHEM. MATER., 1999, 11, 2456-2462). One of these materials,
STA-5 with the BPH topology,
(Mg.sub.2.1Al.sub.11.9P.sub.14O.sub.28), exhibited significant
substitution of Mg.sup.2+ for Al.sup.3+, up to about 15%, but less
substitution than seen in Stucky's non-aqueous ethylene glycol
approach.
[0008] More recently, Lewis et al. developed aqueous solution
chemistry using quaternary ammonium cations leading to high charge
density SAPO, MeAPO, and MeAPSO materials, enabling greater
substitution of SiO.sub.4/2 and [M.sup.2+O.sub.4/2].sup.2- into the
framework for [PO.sub.4/2].sup.+ and [AlO.sub.4/2].sup.-,
respectively, using the ethyltrimethylammonium (ETMA.sup.+) and
diethyldimethylammonium (DEDMA.sup.+) SDAs. These materials include
ZnAPO-57 (U.S. Pat. No. 8,871,178), ZnAPO-59 (U.S. Pat. No.
8,871,177), ZnAPO-67 (U.S. Pat. No. 8,697,927) and MeAPSO-64 (U.S.
Pat. No. 8,696,886). The relationship between the increasing
product charge densities and reaction parameters, namely the
ETMAOH(DEDMAOH)/H.sub.3PO.sub.4 ratios, were outlined in the
literature (see MICROPOROUS AND MESOPOROUS MATERIALS, 189, 2014,
49-63). For the MeAPO compositions, the incorporation of M.sup.2+
observed in these systems was such that for the formulation
[M.sup.2+.sub.xAl.sub.1-xPO.sub.4].sup.x-, x.about.0.3.
[0009] Applicants have now synthesized a new family of highly
charged metallophosphate framework materials, designated PST-17,
with higher charge densities than the MeAPOs of U.S. Pat. No.
4,567,029 and the ZnAPO materials isolated by Lewis. These
metallophosphates are prepared from aqueous solution utilizing a
combination quaternary ammonium and alkali cations. The PST-17
materials have the BPH topology (see DATABASE OF ZEOLITE
STRUCTURES, www.iza-structure.org/databases) and have much higher
metal content than the magnesioaluminophosphate STA-5
(Mg.sub.2.1A.sub.111.9P.sub.14O.sub.28), the above mentioned MeAPO
that has the BPH topology (see CHEM. MATER., 1999, 11, 2456-2462.)
The utility of alkali in MeAPO-based systems is uncommon and in
combination with quaternary ammonium cations under the right
conditions enables this system to achieve the charge densities and
desired midrange compositions between the low charge density MeAPO
and high charge density M.sup.2+-phosphate extremes.
SUMMARY OF THE INVENTION
[0010] As stated, the present invention relates to a new family of
metallophosphate molecular sieves designated PST-17. Accordingly,
one embodiment of the invention is a microporous crystalline
material having a three-dimensional framework of
[M.sup.2+O.sub.4/2].sup.2-, [EO.sub.4/2].sup.- and
[PO.sub.4/2].sup.+ tetrahedral units and an empirical composition
in the as synthesized form and on an anhydrous basis expressed by
an empirical formula of:
R.sup.p+.sub.rA.sup.+.sub.mM.sup.2+.sub.xE.sub.yPO.sub.z
where R is at least one quaternary ammonium cation selected from
the group consisting of ethyltrimethylammonium (ETMA.sup.+),
diethyldimethylammonium (DEDMA.sup.+), hexamethonium (HM.sup.2+),
choline [Me.sub.3NCH.sub.2CH.sub.2OH].sup.+,
trimethylpropylammonium, trimethylbutylammonium,
trimethylisopropylammonium, tetramethylammonium (TMA.sup.+),
tetraethylammonium (TEA.sup.+), tetrapropylammonium (TPA.sup.+) and
mixtures thereof, "r" is the mole ratio of R to P and has a value
of about 0.1 to about 1.0, "p" is the weighted average valence of R
and varies from 1 to 2, A is an alkali metal such as Li.sup.+,
Na.sup.+, K.sup.+, Rb.sup.+ and Cs.sup.+ and mixtures thereof, "m"
is the mole ratio of A to P and varies from 0.1 to 1.0, M is a
divalent element selected from the group of Zn, Mg, Co, Mn and
mixtures thereof, "x" is the mole ratio of M to P and varies from
0.2 to about 0.9, E is a trivalent element selected from the group
consisting of aluminum and gallium and mixtures thereof, "y" is the
mole ratio of E to P and varies from 0.1 to about 0.8 and "z" is
the mole ratio of 0 to P and has a value determined by the
equation:
z=(m+p r+2 x+3 y+5)/2
and is characterized in that it has the x-ray diffraction pattern
having at least the d-spacings and intensities set forth in Table
A:
TABLE-US-00001 TABLE A 2.THETA. d(.ANG.) I/I.sub.0 % 6.90-6.64
12.80-13.31 s-vs 7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w
13.68-13.30 6.47-6.65 w-m 14.95-14.63 5.92-6.05 w 15.64-15.32
5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m
21.5-20.98 4.13-4.23 w-m 24.03-23.58 3.70-3.77 w 24.37-23.97
3.65-3.71 w-s 26.75-26.386 3.33-3.375 w-m 27.51-27.04 3.24-3.295
w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.13 3.12-3.17 w-m
28.87-28.45 3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m
30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.03
2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m
35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w 38.44-37.851
2.34-2.375 w 40.04-39.528 2.25-2.278 w 41.19-40.567 2.19-2.222 w
43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w
[0011] Another embodiment of the invention is a process for
preparing the crystalline metallophosphate molecular sieve
described above. The process comprises forming a reaction mixture
containing reactive sources of R, A, M, E and P and heating the
reaction mixture at a temperature of about 60.degree. C. to about
200.degree. C. for a time sufficient to form the molecular sieve,
the reaction mixture having a composition expressed in terms of
mole ratios of the oxides of:
aR.sub.2/pO:bA.sub.2O:cMO:E.sub.2O.sub.3:dP.sub.2O.sub.5:eH.sub.2O
where "a" has a value of about 2.1 to about 100, "b" has a value of
about 0.1 to about 8.0, "c" has a value of about 0.25 to about 8,
"d" has a value of about 1.69 to about 25, and "e" has a value from
30 to 5000.
[0012] Yet another embodiment of the invention is a hydrocarbon
conversion process using the above-described molecular sieve as a
catalyst. The process comprises contacting at least one hydrocarbon
with the molecular sieve at conversion conditions to generate at
least one converted hydrocarbon.
[0013] Still another embodiment of the invention is a separation
process using the crystalline PST-17 material. The process may
involve separating mixtures of molecular species or removing
contaminants by contacting a fluid with the PST-17 molecular sieve.
Separation of molecular species can be based either on the
molecular size (kinetic diameter) or on the degree of polarity of
the molecular species. Removing contaminants may be by ion exchange
with the molecular sieve.
DETAILED DESCRIPTION OF THE INVENTION
[0014] Applicants have prepared a family of high charge density
crystalline microporous metallophosphate compositions with the BPH
topology, designated PST-17. Compared to other early MeAPO
materials, the PST-17 family of materials contains much more
M.sup.2+and exhibits high framework (FW) charge densities that
unlike the other MeAPOs, use of alkali cations in addition to
organoammonium ions is necessary to balance the FW charge. The
instant microporous crystalline material (PST-17) has an empirical
composition in the as-synthesized form and on an anhydrous basis
expressed by the empirical formula:
R.sup.p+.sub.rA.sup.+.sub.mM.sup.3.degree..sub.xE.sub.yPO.sub.z
where A is at least one alkali cation and is selected from the
group of alkali metals. Specific examples of the A cations include
but are not limited to lithium, sodium, potassium, rubidium, cesium
and mixtures thereof. R is at least one quaternary ammonium cation,
examples of which include but are not limited to
ethyltrimethylammonium (ETMA.sup.+), diethyldimethylammonium
(DEDMA.sup.+), hexamethonium (HM.sup.2+), choline
[Me.sub.3NCH.sub.2CH.sub.2OH].sup.+, trimethylpropylammonium,
trimethylbutylammonium, trimethylisopropylammonium,
tetramethylammonium (TMA.sup.+), tetraethylammonium (TEA),
tetrapropylammonium (TPA.sup.+) and mixtures thereof, and "r" is
the mole ratio of R to P and varies from about 0.1 to about 1.0,
while "p" is the weighted average valence of R and varies from
about 1 to 2. M and E are tetrahedrally coordinated and in the
framework, M is a divalent element selected from the group of Zn,
Mg, Co, Mn and mixtures thereof, while E is a trivalent element
selected from aluminum and gallium and mixtures thereof. The value
of "m" is the mole ratio of A to P and varies from 0.1 to about
1.0, "x" is mole ratio of M to P and varies from 0.2 to about 0.9,
while the ratio of E to P is represented by "y" which varies from
about 0.10 to about 0.8. Lastly, "z" is the mole ratio of O to P
and is given by the equation:
z=(m+p r+2 x+3 y+5)/2.
[0015] When only one type of R organoammonium cation is present,
then the weighted average valence is just the valence of that
cation, e.g., +1 or +2. When more than one R cation is present, the
total amount of R is given by the equation:
R.sub.r.sup.p+=R.sub.r1.sup.(p1)++R.sub.r2.sup.(p2)++R.sub.r2.sup.(p3)++
. . .
the weighted average valence "p" is given by:
p = r 1 p 1 + r 2 p 2 + r 3 p 3 + r 1 + r 2 + r 3 +
##EQU00001##
[0016] It has also been noted that in the PST-17 materials of this
invention that a portion of
[0017] M.sup.2+ may also reside in the pores, likely in a charge
balancing role.
[0018] The microporous crystalline metallophosphate PST-17 is
prepared by a hydrothermal crystallization of a reaction mixture
prepared by combining reactive sources of R, A, E, phosphorous and
M. A preferred form of the PST-17 materials is when E is Al. The
sources of aluminum include but are not limited to aluminum
alkoxides, precipitated aluminas, aluminum metal, aluminum
hydroxide, aluminum salts, alkali aluminates and alumina sols.
Specific examples of aluminum alkoxides include, but are not
limited to aluminum ortho sec-butoxide and aluminum ortho
isopropoxide. Sources of phosphorus include, but are not limited
to, orthophosphoric acid, phosphorus pentoxide, and ammonium
dihydrogen phosphate. Sources of M include but are not limited to
zinc acetate, zinc chloride, cobalt acetate, cobalt chloride,
magnesium acetate, magnesium nitrate, manganese sulfate, manganese
acetate and manganese nitrate. Sources of the other E elements
include but are not limited to precipitated gallium hydroxide,
gallium chloride, gallium sulfate or gallium nitrate. Sources of
the A metals include the halide salts, nitrate salts, hydroxide
salts, acetate salts, and sulfate salts of the respective alkali
metals. R is at least one quaternary ammonium cation selected from
the group consisting of ETMA.sup.+, DEDMA.sup.+, HM.sup.2+,
choline, trimethylpropylammonium, trimethylisopropylammonium,
trimethylbutylammonium, tetramethylammonium (TMA.sup.+),
tetraethylammonium (TEA), tetrapropylammonium (TPA.sup.+) and
mixtures thereof, and the sources include the hydroxide, chloride,
bromide, iodide and fluoride compounds. Specific examples include
without limitation ethyltrimethylammonium hydroxide,
ethyltrimethylammonium chloride, diethyldimethylammonium bromide,
diethyldimethylammonium hydroxide, hexamethonium dihydroxide,
hexamethonium dichloride, choline hydroxide, choline chloride,
trimethylisopropylammonium hydroxide, propyltrimethylammonium
chloride and tetramethylammonium chloride. In one embodiment R is
ETMA.sup.+. In another embodiment, R is diethyldimethylammonium. In
yet another embodiment, R is trimethylisopropylammonium. Finally, R
may also be a combination of ETMA.sup.+and at least one
organoammonium cation selected from the group consisting of
choline, DEDMA.sup.+, TMA.sup.+, HM.sup.2+,
trimethylpropylammonium, trimethylisopropylammonium,
trimethylbutylammonium, TEA.sup.+, and TPA.sup.+.
[0019] The reaction mixture containing reactive sources of the
desired components can be described in terms of molar ratios of the
oxides by the formula:
aR.sub.2/pO:bA.sub.2O:cMO:E.sub.2O.sub.3:dP.sub.2O.sub.5:eH.sub.2O
where "a" varies from about 2.1 to about 100, "b" varies from about
0.1 to about 8, "c" varies from about 0.25 to about 8, "d" varies
from about 1.69 to about 25, and "e" varies from 30 to 5000. If
alkoxides are used, it is preferred to include a distillation or
evaporative step to remove the alcohol hydrolysis products. The
reaction mixture is now reacted at a temperature of about
60.degree. C. to about 200.degree. C. and preferably from about
125.degree. C. to about 175.degree. C. for a period of about 1 day
to about 3 weeks and preferably for a time of about 1 day to about
7 days in a sealed reaction vessel at autogenous pressure. After
crystallization is complete, the solid product is isolated from the
heterogeneous mixture by means such as filtration or
centrifugation, and then washed with deionized water and dried in
air at ambient temperature up to about 100.degree. C. PST-17 seeds
can optionally be added to the reaction mixture in order to
accelerate or otherwise enhance the formation of the desired
microporous composition.
[0020] The PST-17 metallophosphate-based material, which is
obtained from the above-described process, is characterized by the
x-ray diffraction pattern, having at least the d-spacings and
relative intensities set forth in Table A below.
TABLE-US-00002 TABLE A 2.THETA. d(.ANG.) I/I.sub.0 % 6.90-6.64
12.80-13.31 s-vs 7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w
13.68-13.3 6.47-6.65 w-m 14.95-14.63 5.92-6.05 w 15.64-15.32
5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m
21.50-20.98 4.13-4.23 w-m 24.03-23.58 3.70-3.77 w 24.37-23.97
3.65-3.71 w-s 26.75-26.386 3.33-3.375 w-m 27.51-27.04 3.24-3.295
w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.13 3.12-3.17 w-m
28.87-28.45 3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m
30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.03
2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m
35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w 38.44-37.851
2.34-2.375 w 40.04-39.528 2.25-2.278 w 41.19-40.567 2.19-2.222 w
43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w
[0021] The PST-17 may be modified in many ways to tailor it for use
in a particular application. Modifications include calcination,
ammonia calcinations, ion-exchange, steaming, various acid
extractions, ammonium hexafluorosilicate treatment, or any
combination thereof, as outlined for the case of UZM-4 in U.S. Pat.
No. 6,776,975 which is incorporated by reference in its entirety.
In addition, properties that may be modified include porosity,
adsorption, framework composition, acidity, thermal stability,
ion-exchange capacity, etc.
[0022] As synthesized, the PST-17 material will contain some of the
exchangeable or charge balancing cations in its pores. These
exchangeable cations can be exchanged for other cations, or in the
case of organic cations, they can be removed by heating under
controlled conditions. Because PST-17 is a large pore material, the
BPH structure has 12-ring pores along the c-axis, many organic
cations may be removed directly by ion-exchange, heating may not be
necessary. A preferred method of removing organic cations from the
pores is ammonia calcination. Calcination in air converts the
organic cations in the pores to protons, which can lead to the loss
of some metal, for example A1, from the framework upon exposure to
ambient atmospheric water vapor. When the calcination is carried
out in an ammonia atmosphere, the organic cation in the pore is
replaced by NH4.sup.+ cation and the framework remains intact (see
STUDIES IN SURFACE SCIENCE, (2004) vol. 154, p. 1324-1331). Typical
conditions for ammonia calcinations include the use of gaseous
anhydrous ammonia flowing at a rate of 1.1 Umin while ramping the
sample temperature at 5.degree. C./min to 500.degree. C. and
holding at that temperature for a time ranging from 5 minutes to an
hour. The resulting ammonium/alkali form of PST-17 has essentially
the diffraction pattern of Table A. Once in this form, the ammonia
calcined material may be ion-exchanged with H.sup.+, NH4.sup.+,
alkali metals, alkaline earth metals, transition metals, rare earth
metals, or any mixture thereof, to achieve a wide variety of
compositions with the PST-17 framework in superior condition.
[0023] When PST-17 or its modified forms are calcined in air, there
can be a loss of metal from the framework, such as Al, which can
alter the x-ray diffraction pattern from that observed for the
as-synthesized PST-17 (see STUDIES IN SURFACE SCIENCE, (2004) vol.
154, p.1324-1331). Typical conditions for the calcination of the
PST-17 sample include ramping the temperature from room temperature
to a calcination temperature of 400.degree. to 600.degree. C.,
preferably a calcination temperature of 450.degree. to 550.degree.
C. at a ramp rate of 1 to 5.degree. C./min, preferably a ramp rate
of 2 to 4.degree. C./min, the temperature ramp conducted in an
atmosphere consisting either of flowing nitrogen or flowing clean
dry air, preferably an atmosphere of flowing nitrogen. Once at the
desired calcination temperature, if the calcination atmosphere
employed during the temperature ramp is flowing clean dry air, it
may remain flowing clean dry air. If the calcination atmosphere
during the ramp was flowing nitrogen, it may remain flowing
nitrogen at the calcination temperature or it may be immediately
converted to clean dry air; preferably at the calcination
temperature the calcination atmosphere will remain flowing nitrogen
for a period of 1-10 hours and preferably for a period of 2-4 hours
before converting the calcination atmosphere to flowing clean dry
air. The final step of the calcination is a dwell at the
calcination temperature in clean dry air. Whether the calcination
atmosphere during the initial temperature ramp was flowing nitrogen
or flowing clean dry air, once at the calcination temperature and
once the calcination atmosphere is clean dry air, the PST-17 sample
will spend a period of 1-24 hours and preferably a period of 2-6
hours under these conditions to complete the calcination
process.
[0024] The crystalline PST-17 materials of this invention can be
used for separating mixtures of molecular species, removing
contaminants through ion exchange and catalyzing various
hydrocarbon conversion processes. Separation of molecular species
can be based either on the molecular size (kinetic diameter) or on
the degree of polarity of the molecular species.
[0025] The PST-17 compositions of this invention can also be used
as a catalyst or catalyst support in various hydrocarbon conversion
processes. Hydrocarbon conversion processes are well known in the
art and include cracking, hydrocracking, alkylation of both
aromatics and isoparaffin, isomerization, polymerization,
reforming, hydrogenation, dehydrogenation, transalkylation,
dealkylation, hydration, dehydration, hydrotreating,
hydrodenitrogenation, hydrodesulfurization, methanol to olefins,
methanation and syngas shift process. Specific reaction conditions
and the types of feeds which can be used in these processes are set
forth in U.S. Pat. No. 4,310,440, U.S. Pat. No. 4,440,871 and U.S.
Pat. No. 5,126,308, which are incorporated by reference. Preferred
hydrocarbon conversion processes are those in which hydrogen is a
component such as hydrotreating or hydrofining, hydrogenation,
hydrocracking, hydrodenitrogenation, hydrodesulfurization, etc.
[0026] Hydrocracking conditions typically include a temperature in
the range of 400.degree. to 1200.degree. F. (204-649.degree. C.),
preferably between 600.degree. and 950.degree. F. (316-510.degree.
C.). Reaction pressures are in the range of atmospheric to about
3,500 psig (24,132 kPa g), preferably between 200 and 3000 psig
(1379 to 20,685 kPa g). Contact times usually correspond to liquid
hourly space velocities (LHSV) in the range of about 0.1 hr.sup.-1
to 15 hr.sup.-1, preferably between about 0.2 and 3 hr.sup.-1.
Hydrogen circulation rates are in the range of 1,000 to 50,000
standard cubic feet (scf) per barrel of charge (178-8,888 std.
m.sup.3/m.sup.3), preferably between 2,000 and 30,000 scf per
barrel of charge (355-5,333 std. m.sup.3/m.sup.3). Suitable
hydrotreating conditions are generally within the broad ranges of
hydrocracking conditions set out above.
[0027] The reaction zone effluent is normally removed from the
catalyst bed, subjected to partial condensation and vapor-liquid
separation and then fractionated to recover the various components
thereof. The hydrogen, and if desired some or all of the
unconverted heavier materials, are recycled to the reactor.
Alternatively, a two-stage flow may be employed with the
unconverted material being passed into a second reactor. Catalysts
of the subject invention may be used in just one stage of such a
process or may be used in both reactor stages.
[0028] Catalytic cracking processes are preferably carried out with
the PST-17 composition using feedstocks such as gas oils, heavy
naphthas, deasphalted crude oil residua, etc. with gasoline being
the principal desired product. Temperature conditions of
850.degree. to 1100.degree. F. (455.degree. C. to 593.degree. C.),
LHSV values of 0.5 hr.sup.-1 to 10 hr.sup.-1 and pressure
conditions of from about 0 to 50 psig (0-345 kPa) are suitable.
[0029] Alkylation of aromatics usually involves reacting an
aromatic (C.sub.2 to C.sub.12), especially benzene, with a
monoolefin to produce a linear alkyl substituted aromatic. The
process is carried out at an aromatic: olefin (e.g.,
benzene:olefin) ratio of between 5:1 and 30:1, a LHSV of about 0.3
to about 6 hr.sup.-1, a temperature of about 100.degree. to about
250.degree. C. and pressures of about 200 to about 1000 psig (1,379
to 6,895 kPa). Further details on apparatus may be found in U.S.
Pat. No. 4,870,222 which is incorporated by reference.
[0030] Alkylation of isoparaffins with olefins to produce alkylates
suitable as motor fuel components is carried out at temperatures of
-30.degree. to 40.degree. C., pressures from about atmospheric to
about 6,894 kPa (1,000 psig) and a weight hourly space velocity
(WHSV) of 0.1 hr.sup.-1 to about 120 hr.sup.-1. Details on paraffin
alkylation may be found in U.S. Pat. No. 5,157,196 and U.S. Pat.
No. 5,157,197, which are incorporated by reference.
[0031] The conversion of methanol to olefins is effected by
contacting the methanol with the PST-17 catalyst at conversion
conditions, thereby forming the desired olefins. The methanol can
be in the liquid or vapor phase with the vapor phase being
preferred. Contacting the methanol with the PST-17 catalyst can be
done in a continuous mode or a batch mode with a continuous mode
being preferred. The amount of time that the methanol is in contact
with the PST-17 catalyst must be sufficient to convert the methanol
to the desired light olefin products. When the process is carried
out in a batch process, the contact time varies from about 0.001
hour to about 1 hour and preferably from about 0.01 hour to about
1.0 hour. The longer contact times are used at lower temperatures
while shorter times are used at higher temperatures. Further, when
the process is carried out in a continuous mode, the Weight Hourly
Space Velocity (WHSV) based on methanol can vary from about 1
hr.sup.-1 to about 1000 hr.sup.-1 and preferably from about 1
hr.sup.-1 to about 100 hr.sup.-1.
[0032] Generally, the process must be carried out at elevated
temperatures in order to form light olefins at a fast enough rate.
Thus, the process should be carried out at a temperature of about
300.degree. C. to about 600.degree. C., preferably from about
400.degree. C. to about 550.degree. C. and most preferably from
about 450.degree. C. to about 525.degree. C. The process may be
carried out over a wide range of pressure including autogenous
pressure. Thus, the pressure can vary from about 0 kPa (0 psig) to
about 1724 kPa (250 psig) and preferably from about 34 kPa (5 psig)
to about 345 kPa (50 psig).
[0033] Optionally, the methanol feedstock may be diluted with an
inert diluent in order to more efficiently convert the methanol to
olefins. Examples of the diluents which may be used are helium,
argon, nitrogen, carbon monoxide, carbon dioxide, hydrogen, steam,
paraffinic hydrocarbons, e. g., methane, aromatic hydrocarbons, e.
g., benzene, toluene and mixtures thereof. The amount of diluent
used can vary considerably and is usually from about 5 to about 90
mole percent of the feedstock and preferably from about 25 to about
75 mole percent.
[0034] The actual configuration of the reaction zone may be any
well known catalyst reaction apparatus known in the art. Thus, a
single reaction zone or a number of zones arranged in series or
parallel may be used. In such reaction zones the methanol feedstock
is flowed through a bed containing the PST-17 catalyst. When
multiple reaction zones are used, one or more PST-17 catalysts may
be used in series to produce the desired product mixture. Instead
of a fixed bed, a dynamic bed system, e. g., fluidized or moving,
may be used. Such a dynamic system would facilitate any
regeneration of the PST-17 catalyst that may be required. If
regeneration is required, the PST-17 catalyst can be continuously
introduced as a moving bed to a regeneration zone where it can be
regenerated by means such as oxidation in an oxygen containing
atmosphere to remove carbonaceous materials.
[0035] The following examples are presented in illustration of this
invention and are not intended as undue limitations on the
generally broad scope of the invention as set out in the appended
claims. The products of this invention are designated with the
general name PST-17, with the understanding that all of the PST-17
materials exhibit a structure with the BPH topology.
[0036] The structure of the PST-17 compositions of this invention
was determined by x-ray analysis. The x-ray patterns presented in
the following examples were obtained using standard x-ray powder
diffraction techniques. The radiation source was a high-intensity,
x-ray tube operated at 45 kV and 35 mA. The diffraction pattern
from the copper K-alpha radiation was obtained by appropriate
computer based techniques. Flat compressed powder samples were
continuously scanned at 2.degree. to 56.degree. (2.theta.).
Interplanar spacings (d) in Angstrom units were obtained from the
position of the diffraction peaks expressed as .theta. where
.theta. is the Bragg angle as observed from digitized data.
Intensities were determined from the integrated area of diffraction
peaks after subtracting background, "I.sub.0" being the intensity
of the strongest line or peak, and "I" being the intensity of each
of the other peaks.
[0037] As will be understood by those skilled in the art the
determination of the parameter 2.theta. is subject to both human
and mechanical error, which in combination can impose an
uncertainty of about .+-.0.4.degree. on each reported value of
2.theta.. This uncertainty is, of course, also manifested in the
reported values of the d-spacings, which are calculated from the
2.theta. values. This imprecision is general throughout the art and
is not sufficient to preclude the differentiation of the present
crystalline materials from each other and from the compositions of
the prior art. In some of the x-ray patterns reported, the relative
intensities of the d-spacings are indicated by the notations vs, s,
m, and w which represent very strong, strong, medium, and weak,
respectively. In terms of 100.times.I/I.sub.0, the above
designations are defined as: [0038] w=0-15; m=15-60: s=60-80 and
vs=80-100
[0039] In certain instances the purity of a synthesized product may
be assessed with reference to its x-ray powder diffraction pattern.
Thus, for example, if a sample is stated to be pure, it is intended
only that the x-ray pattern of the sample is free of lines
attributable to crystalline impurities, not that there are no
amorphous materials present.
[0040] In order to more fully illustrate the invention, the
following examples are set forth. It is to be understood that the
examples are only by way of illustration and are not intended as an
undue limitation on the broad scope of the invention as set forth
in the appended claims.
Example 1
[0041] A Teflon beaker was charged with 150.00 g
ethyltrimethylammonium hydroxide (ETMAOH, 20%, SACHEM, Inc.) and
placed under a high speed stirring apparatus. Pre-ground aluminum
isopropoxide (13.3% Al), 4.82 g, was added to the reaction mixture
and dissolved with stirring. This was followed by the dropwise
addition of 16.31 g H.sub.3PO.sub.4 (85.7%). Separately, 5.22 g
Zn(OAc).sub.2*2H.sub.2O was dissolved in 20.50 g de-ionized water
and the resulting solution was added to the reaction mixture in a
dropwise fashion. After completion of the addition, the reaction
mixture was homogenized for an hour. Then, a solution was prepared
by dissolving 1.17 g KOAc (99.4%) in 10.00 g de-ionized water. This
was added to the reaction mixture in a dropwise fashion and the
reaction mixture was homogenized for an additional 20 minutes
post-addition. The reaction mixture was distributed among 7
Teflon-lined autoclaves and digested at autogenous pressures at
temperatures of 95.degree., 125.degree., 150.degree., and
175.degree. C., for either 40 or 167 hours or both. The solid
products were isolated by centrifugation and washed with de-ionized
water. All of the products were identified as PST-17 by powder
x-ray diffraction, except for the product 175.degree. C./167 hour
digestion, which also contained a significant impurity. The
representative diffraction lines of which are shown in Table 1
below for the sample from the 125.degree. C./167 hour digestion.
Elemental analysis of this same product showed it was composed of
the elemental ratios Al/P=0.31, Zn/P=0.70, K/P=0.37, and N/P=0.21,
consistent with the stoichiometry
ETMA.sub.0.21K.sub.0.37Zn.sub.0.70Al.sub.0.31P.
TABLE-US-00003 TABLE 1 2-.THETA. d(.ANG.) I/I.sub.0 (%) 6.69 13.19
vs 7.54 11.72 m 13.10 6.76 w 13.40 6.60 w 14.701 6.02 w 15.39 5.75
w 18.76 4.73 w 20.14 4.41 m 21.14 4.20 m 23.75 3.74 w 24.08 3.69 m
26.50 3.36 w 27.20 3.28 w 27.43 3.25 w 28.26 3.16 w 28.56 3.12 w
29.66 3.01 m 30.08 2.97 m 30.52 2.93 w 31.06 2.88 w 31.26 2.86 w
33.31 2.69 w 33.82 2.65 w 34.25 2.62 w 35.08 2.56 w 35.74 2.51 w
36.48 2.46 w 38.02 2.36 w 38.85 2.32 w 39.21 2.30 w 39.72 2.27 w
40.76 2.21 w 42.98 2.10 w 43.42 2.08 w 47.37 1.92 w 48.84 1.86 w
49.54 1.84 w 50.14 1.82 w 51.10 1.79 w 53.06 1.72 w 53.38 1.72 w
53.96 1.70 w 55.60 1.65 w
Example 2
[0042] A Teflon beaker was charged with 174.00 g
Diethyldimethylammonium hydroxide (DEDMAOH, 20% aqueous, SACHEM,
Inc.) and placed under a high speed mixer. Pre-ground aluminum
isopropoxide (13.2% Al), 4.97 g, was added to the reaction mixture
and stirred until dissolved. This was followed by the dropwise
addition of 16.69 g H.sub.3PO.sub.4 (85.7%). Separately,
Zn(OAc).sub.2*2H.sub.2O, 5.34 g, was dissolved in 25.00 g
de-ionized water. This solution was added dropwise to the reaction
mixture with vigorous stirring to homogenize. An additional
solution was prepared by dissolving KOAc (99.4%), 1.19 g, in 12.88
g de-ionized water. This solution was added dropwise to the
reaction mixture and stirred for an hour. The reaction mixture was
distributed among 7 Teflon-lined autoclaves and digested at
autogenous pressures at temperatures of 95.degree., 125.degree.,
150.degree., and 175.degree. C., for either 48, 136 hr, or 170
hours. The solid products were isolated by centrifugation and
washed with de-ionized water. With the exception of the product of
the 95.degree. C./170 hour digestion, all of the products were
found to contain PST-17 by powder x-ray diffraction. The
representative diffraction lines are shown in Table 2 below for the
PST-17 products from the 125.degree. C./48 hour (Table 2a) and
175.degree. C./136 hour (Table 2b) digestions. Elemental analysis
of these same products showed they were composed of the following
elemental ratios, 125.degree. C./48 hr: Al/P=0.36, Zn/P=0.75,
K/P=0.36, and N/P=0.25, consistent with the stoichiometry
DEDMA.sub.0.25K.sub.0.36Zn.sub.0.75Al.sub.0.36P and 175.degree.
C./136 hr: Al/P=0.39, Zn/P=0.60, K/P=0.26, and N/P=0.31, consistent
with the stoichiometry
DEDMA.sub.0.31K.sub.0.26Zn.sub.0.60Al.sub.0.39P.
TABLE-US-00004 TABLE 2 Table 2a Table 2b 2-.THETA. d(.ANG.)
I/I.sub.0 (%) 2-.THETA. d(.ANG.) I/I.sub.0 (%) 6.70 13.19 vs 6.72
13.14 s 7.54 11.72 s 7.56 11.69 vs 13.06 6.77 w 10.11 8.75 w 13.40
6.60 w 13.11 6.75 w 14.71 6.02 w 13.44 6.58 w 15.40 5.75 m 14.74
6.01 w 18.76 4.73 m 15.44 5.74 m 20.02 4.43 w 16.56 5.35 w 20.18
4.40 m 18.76 4.72 m 21.12 4.20 m 20.22 4.39 m 23.73 3.75 w 21.18
4.19 m 24.12 3.69 m 23.78 3.74 w 26.32 3.38 w 24.18 3.68 m 26.48
3.36 w 26.54 3.36 m 27.18 3.28 w 27.24 3.27 m 27.42 3.25 w 27.44
3.25 w 28.24 3.16 w 28.28 3.15 m 28.56 3.12 w 28.64 3.11 m 29.64
3.01 m 29.70 3.01 m 30.12 2.96 m 30.18 2.96 m 30.58 2.92 m 30.64
2.92 m 31.08 2.88 w 31.20 2.86 w 31.22 2.86 w 33.36 2.68 m 33.28
2.69 w 33.90 2.64 m 33.84 2.65 m 34.36 2.61 w 34.27 2.61 w 35.14
2.55 w 35.04 2.56 w 35.73 2.51 w 35.72 2.51 w 36.08 2.49 w 36.50
2.46 w 36.58 2.45 w 38.09 2.36 w 38.14 2.36 w 39.22 2.30 w 38.93
2.31 w 39.72 2.27 w 39.82 2.26 w 39.96 2.25 w 40.84 2.21 w 40.78
2.21 w 42.97 2.10 w 41.29 2.18 w 43.54 2.08 w 42.92 2.11 w 44.10
2.05 w 43.46 2.08 w 44.33 2.04 w 44.20 2.05 w 47.53 1.91 w 46.45
1.95 w 48.38 1.88 w 48.88 1.86 w 48.98 1.86 w 49.52 1.84 w 49.56
1.84 w 50.18 1.82 w 50.33 1.81 w 51.04 1.79 w 51.14 1.78 w 53.02
1.73 w 53.12 1.72 w 53.37 1.72 w 53.48 1.71 w 53.93 1.70 w 54.10
1.69 w 55.24 1.66 w 55.30 1.66 w 55.69 1.65 w
Example 3
[0043] A Teflon bottle was charged with 159.12 g ETMAOH (20%)
followed by the addition of 6.31 g of Al-isopropoxide
(Al(OiPr).sub.3, 98+%). The mixture was stirred in a sealed bottle
until the Al(OiPr).sub.3 was fully dissolved. The mixture was
transferred to a Teflon beaker equipped with an overhead high speed
stirrer. Then, H.sub.3PO.sub.4 (85%), 20.95 g, was added slowly
with vigorous mixing. Separately, 6.78 g Zn acetate dihydrate was
dissolved in 30 g deionized water. The Zn solution was then slowly
added to the Al/P/ETMAOH solution over a period of 30 minutes while
mixing continued. Homogenization of the reaction mixture was
continued for 30 minutes after completion of the Zn addition. In a
separate beaker, 1.82 g KBr was dissolved in 25.03 g deionized
water. This was then added slowly to the reaction mixture while
continuing to mix. Again, mixing was continued for 30 minutes after
this addition was completed. A clear solution reaction mixture was
then distributed between 4.times.125 ml autoclaves and digested for
7 and 8 d at 150.degree. C. The solid products were isolated by
centrifugation and washed with de-ionized water. Powder X-ray
diffraction showed all of the products to be PST-17 with the BPH
topology. Representative diffraction lines for the PST-17 product
are given in Table 3 below.
TABLE-US-00005 TABLE 3 2.THETA. d(.ANG.) I/I.sub.0 % 6.83 12.94 vs
7.69 11.49 m 10.24 8.63 w 13.24 6.68 w 13.55 6.53 w 14.87 5.95 w
15.55 5.70 w 18.92 4.69 w 20.30 4.37 w 21.32 4.16 w 23.91 3.72 w
24.27 3.66 m 26.66 3.34 w 27.38 3.25 w 27.60 3.23 w 28.46 3.13 w
28.76 3.10 w 29.84 2.99 w 30.26 2.95 m 30.77 2.90 w 31.27 2.86 w
31.43 2.84 w 33.51 2.67 w 34.02 2.63 w 35.26 2.54 w 36.68 2.45 w
38.24 2.35 w 39.85 2.26 w 40.14 2.24 w 40.97 2.20 w 43.22 2.09 w
43.62 2.07 w
Example 4 Na.sup.+ Ion-Exchange of PST-17
[0044] A Na.sup.+ ion-exchange was carried out on the product from
the 7 d at 150.degree. C. reaction in Example 3. A 1.75 g portion
of the dried PST-17 was slurried in 29.2 g of a 6% NaCl solution.
The slurry was covered and heated to 75.degree. C. while mixing on
a stir plate. The slurry was held at 75.degree. C. for about 1
hour. The solid was then collected and washed with deionized water.
This process was repeated two additional times. The solid was dried
at 100.degree. C. after the final exchange step. A Leco CHN
analysis showed that the C level was reduced to 2.75 wt % after the
exchange, where typically as-synthesized PST-17 contains 6.5 to 11%
carbon. This demonstrates that significant portions of the organic
cation may be removed directly by ion-exchange.
Example 5 NH4.sup.+ Ion-Exchange of PST-17
[0045] A Teflon bottle was charged with 891.07 g ETMAOH (20%,
SACHEM, Inc.). A 35.31 g portion of aluminum isopropoxide (AIP,
98+%) was added and the mixture was stirred in the sealed bottle
until the AIP was fully dissolved. The reaction mixture was
transferred to a Teflon beaker and 117.32 g of H.sub.3PO.sub.4
(85%) was added slowly while mixing with an overhead stirrer.
Separately, 37.95 g of zinc acetate dehydrate was dissolved in
168.00 g of deionized water. The zinc acetate solution was then
slowly added to the reaction mixture over a period of 2 hours,
while mixing with an overhead stirrer. The mixing was continued for
30 min after the addition was completed. In a separate beaker,
10.18 g KBr was dissolved in 25.03 g deionized water. This was then
added slowly to the reaction mixture while continuing to mix with
an overhead stirrer. The mixing was continued for 30 min after this
addition was complete. A slightly hazy solution resulted. The
solution was then transferred to a 2 L autoclave and digested for 7
days at 150.degree. C. at autogenous pressure. The product was
isolated by centrifugation, washed with deionized water and dried
at 100.degree. C. Powder x-ray diffraction showed the product to be
PST-17 with the BPH topology. Representative diffraction lines for
the PST-17 product are shown in Table 4a below. Elemental analysis
showed the PST-17 to consist of the following elemental ratios:
Al/P=0.32, Zn/P=0.71, K/P=0.37, and N/P=0.25, consistent with the
empirical formula ETMA.sub.0.25K.sub.0.37Zn.sub.0.71Al.sub.0.32P.
Specifically, the carbon content in this PST-17 was 7.56%.
[0046] A 20 g portion of the as-synthesized PST-17 material was
then ammonium ion-exchanged. A 20 g portion of NH.sub.4NO.sub.3 was
dissolved in 200 g deionized water. The dried PST-17 material was
then added to this solution while mixing on a magnetic stir plate.
The slurry was covered and heated to 75.degree. C. for 1.5 hours.
The solid was collected and washed by filtration. The exchange
procedure was repeated two additional times. The solid was dried at
100.degree. C. after the final exchange step. The ammonium
ion-exchanged PST-17 was identified as such by powder x-ray
diffraction; the representative diffraction lines shown in Table
4b. Leco CHN analysis showed that the carbon content in the
ammonium ion-exchanged PST-17 is 0.21%, indicating that more than
97% of the ETMA.sup.+ SDA had been removed by ion-exchange.
TABLE-US-00006 TABLE 4 Table 4a Table 4b 2-.THETA. d(.ANG.)
I/I.sub.0 % 2-.THETA. d(.ANG.) I/I.sub.0 % 6.72 13.15 vs 6.73 13.12
vs 7.58 11.65 m 7.61 11.61 s 10.13 8.72 w 10.15 8.71 w 13.14 6.73 w
13.19 6.71 w 13.45 6.58 w 13.46 6.57 m 14.76 6.00 w 14.81 5.98 w
15.44 5.73 w 15.47 5.72 w 16.60 5.34 w 18.86 4.70 w 18.82 4.71 w
20.22 4.39 w 20.20 4.39 w 21.29 4.17 m 21.21 4.18 w 23.89 3.72 w
22.84 3.89 w 24.21 3.67 m 24.16 3.68 m 26.63 3.35 w 26.58 3.35 w
27.08 3.29 w 27.27 3.27 w 27.38 3.25 w 27.51 3.24 w 27.62 3.23 w
28.35 3.15 w 28.44 3.14 w 28.63 3.12 w 28.68 3.11 w 29.74 3.00 w
29.82 2.99 m 30.15 2.96 m 30.19 2.96 m 30.63 2.92 w 30.71 2.91 w
31.34 2.85 w 31.16 2.87 w 33.41 2.68 w 31.41 2.85 w 33.90 2.64 w
33.53 2.67 w 35.16 2.55 w 33.96 2.64 w 35.84 2.50 w 34.23 2.62 w
36.53 2.46 w 34.44 2.60 w 38.12 2.36 w 35.30 2.54 w 38.93 2.31 w
36.60 2.45 w 39.34 2.29 w 38.21 2.35 w 39.78 2.26 w 39.83 2.26 w
40.85 2.21 w 40.93 2.20 w 43.07 2.10 w 43.19 2.09 w 43.48 2.08 w
43.58 2.07 w 44.25 2.05 w 46.14 1.97 w 46.02 1.97 w 49.77 1.83 w
46.57 1.95 w 51.36 1.78 w 48.97 1.86 w 53.32 1.72 w 49.62 1.84 w
55.70 1.65 w 50.21 1.82 w 50.66 1.80 w 51.18 1.78 w 51.69 1.77 w
53.15 1.72 w 53.44 1.71 w 54.04 1.70 w
Specific Embodiments
[0047] While the following is described in conjunction with
specific embodiments, it will be understood that this description
is intended to illustrate and not limit the scope of the preceding
description and the appended claims.
[0048] A first embodiment of the invention is a microporous
crystalline metallophosphate material having a three-dimensional
framework of M.sup.2+O.sub.4/2].sup.2-, [EO.sub.4/2].sup.- and
[PO.sub.4/2].sup.+ tetrahedral units and an empirical composition
in the as synthesized form and anhydrous basis expressed by an
empirical formula of
R.sup.p+.sub.rA.sup.+.sub.mM.sup.2+.sub.xE.sub.yPO.sub.z where R is
at least one quaternary ammonium cation selected from the group
consisting of ethyltrimethylammonium (ETMA.sup.+),
diethyldimethylammonium (DEDMA.sup.+), hexamethonium (HM.sup.2+),
choline [Me.sub.3NCH.sub.2CH.sub.2OH].sup.+,
trimethylpropylammonium, trimethylbutylammonium,
trimethylisopropylammonium, tetramethylammonium (TMA.sup.+),
tetraethylammonium (TEA.sup.+), tetrapropylammonium (TPA.sup.+) and
mixtures thereof, "r" is the mole ratio of R to P and has a value
of about 0.1 to about 1.0, "p" is the weighted average valence of R
and varies from 1 to 2, A is an alkali metal selected from the
group consisting of Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+ and
Cs.sup.+ and mixtures thereof, "m" is the mole ratio of A to P and
varies from 0.1 to 1.0, M is a divalent element selected from the
group of Zn, Mg, Co, Mn and mixtures thereof, "x" is the mole ratio
of M to P and varies from 0.2 to about 0.9, E is a trivalent
element selected from the group consisting of aluminum and gallium
and mixtures thereof, "y" is the mole ratio of E to P and varies
from 0.1 to about 0.8 and "z" is the mole ratio of O to P and has a
value determined by the equation z=(m+p r+2 x+3 y+5)/2 and is
characterized in that it has the x-ray diffraction pattern having
at least the d-spacings and intensities set forth in Table A
TABLE-US-00007 TABLE A 2.THETA. d(.ANG.) I/I.sub.0 % 6.90-6.64
12.80-13.31 s-vs 7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w
13.68-13.30 6.47-6.65 w-m 14.95-14.63 5.92-6.05 w 15.64-15.32
5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m
21.5-20.98 4.13-4.23 w-m 24.03-23.58 3.70-3.77 w 24.37-23.97
3.65-3.71 w-s 26.75-26.386 3.33-3.375 w-m 27.51-27.04 3.24-3.295
w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.13 3.12-3.17 w-m
28.87-28.45 3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m
30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.03
2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m
35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w 38.44-37.851
2.34-2.375 w 40.04-39.528 2.25-2.278 w 41.19-40.567 2.19-2.222 w
43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w
[0049] An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the first embodiment in
this paragraph where in the metallophosphate material A is
potassium. An embodiment of the invention is one, any or all of
prior embodiments in this paragraph up through the first embodiment
in this paragraph where in the metallophosphate material R is
ethyltrimethylammonium cation, ETMA.sup.+. An embodiment of the
invention is one, any or all of prior embodiments in this paragraph
up through the first embodiment in this paragraph where in the
metallophosphate material R is the diethyldimethylammonium cation,
DEDMA.sup.+. An embodiment of the invention is one, any or all of
prior embodiments in this paragraph up through the first embodiment
in this paragraph where in the metallophosphate material R is the
trimethylisopropylammonium cation. An embodiment of the invention
is one, any or all of prior embodiments in this paragraph up
through the first embodiment in this paragraph where a crystalline
modified form of the crystalline microporous metallophosphate
comprises a three-dimensional framework of
[M.sup.2+O.sub.4/2].sup.2-, [EO.sub.4/2].sup.- and
[PO.sub.4/2].sup.+ tetrahedral units and derived by modifying the
crystalline microporous metallophosphate, the modifications
comprising calcination, ammonia calcinations, ion-exchange,
steaming, various acid extractions, ammonium hexafluorosilicate
treatment, or any combination thereof.
[0050] A second embodiment of the invention is a method for
preparing a microporous crystalline metallophosphate material
having a three-dimensional framework of [M.sup.2+O.sub.4/2].sup.2-,
[EO.sub.4/2].sup.- and [PO.sub.4/2].sup.+ tetrahedral units and an
empirical composition in the as synthesized form and anhydrous
basis expressed by an empirical formula of
R.sup.p+.sub.rA.sup.+.sub.mM.sup.2+.sub.xE.sub.yPO.sub.z where R is
at least one quaternary ammonium cation selected from the group
consisting of ethyltrimethylammonium (ETMA.sup.+),
diethyldimethylammonium (DEDMA.sup.+), hexamethonium (HM.sup.2+),
choline [Me.sub.3NCH.sub.2CH.sub.2OH].sup.+,
trimethylpropylammonium, trimethylbutylammonium,
trimethylisopropylammonium, tetramethylammonium (TMA.sup.+),
tetraethylammonium (TEA.sup.+), tetrapropylammonium (TPA.sup.+) and
mixtures thereof, "r" is the mole ratio of R to P and has a value
of about 0.1 to about 1.0, "p" is the weighted average valence of R
and varies from 1 to 2, A is an alkali metal selected from the
group consisting of Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+and
Cs.sup.+ and mixtures thereof, "m" is the mole ratio of A to P and
varies from 0.1 to 1.0, M is a divalent element selected from the
group of Zn, Mg, Co, Mn and mixtures thereof, "x" is the mole ratio
of M to P and varies from 0.2 to about 0.9, E is a trivalent
element selected from the group consisting of aluminum and gallium
and mixtures thereof, "y" is the mole ratio of E to P and varies
from 0.1 to about 0.8 and "z" is the mole ratio of O to P and has a
value determined by the equation z=(m+p r+2 x+3 y+5)/2 and is
characterized in that it has the x-ray diffraction pattern having
at least the d-spacings and intensities set forth in Table A
TABLE-US-00008 TABLE A 2.THETA. d(.ANG.) I/I.sub.0 % 6.90-6.64
12.80-13.31 s-vs 7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w
13.68-13.30 6.47-6.65 w-m 14.95-14.63 5.92-6.05 w 15.64-15.32
5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m
21.5-20.98 4.13-4.23 w-m 24.03-23.58 3.70-3.77 w 24.37-23.97
3.65-3.71 w-s 26.75-26.386 3.33-3.375 w-m 27.51-27.04 3.24-3.295
w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.13 3.12-3.17 w-m
28.87-28.45 3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m
30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.03
2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m
35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w 38.44-37.851
2.34-2.375 w 40.04-39.528 2.25-2.278 w 41.19-40.567 2.19-2.222 w
43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w
the process comprising forming a reaction mixture containing
reactive sources of R, A, E, M and P, and heating the reaction
mixture at a temperature of about 60.degree. C. to about
200.degree. C. for a time sufficient to form the metallophosphate
molecular sieve, the reaction mixture having a composition
expressed in terms of mole ratios of the oxides of aR.sub.2/pO
bA.sub.2O cMO E.sub.2O.sub.3 dP.sub.2O.sub.5 eH.sub.2O where "a"
has a value of about 2.1 to about 100, "b" has a value of about 0.1
to about 8.0, "c" has a value of about 0.25 to about 8, "d" has a
value of about 1.69 to about 25, and "e" has a value from 30 to
5000. An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the second embodiment in
this paragraph where the initial reaction mixture is a clear
solution before digestion. An embodiment of the invention is one,
any or all of prior embodiments in this paragraph up through the
second embodiment in this paragraph where A is selected from the
group consisting of Li.sup.+, Na.sup.+, K.sup.+, Rb.sup.+ and
Cs.sup.+and mixtures thereof and the source of A is selected from
the group consisting of halide salts, nitrate salts, acetate salts,
sulfate salts, hydroxide salts and mixtures thereof. An embodiment
of the invention is one, any or all of prior embodiments in this
paragraph up through the second embodiment in this paragraph where
M is selected from the group consisting of Zn.sup.2+, Mn.sup.2+,
Co.sup.2+ and Mg.sup.2+ and mixtures thereof and where the source
of M is selected from the group consisting of halide salts, nitrate
salts, acetate salts, sulfate salts and mixtures thereof. An
embodiment of the invention is one, any or all of prior embodiments
in this paragraph up through the second embodiment in this
paragraph where the source of E is selected from the group
consisting of aluminum isopropoxide, aluminum sec-butoxide,
precipitated alumina, Al(OH).sub.3, alkali aluminate salts,
aluminum metal, aluminum halide salts, aluminum sulfate salts,
aluminum nitrate salts, precipitated gallium oxyhydroxide, gallium
nitrate, gallium sulfate and mixtures thereof. An embodiment of the
invention is one, any or all of prior embodiments in this paragraph
up through the second embodiment in this paragraph where the
reaction mixture is reacted at a temperature of about 125.degree.
C. to about 185.degree. C. for a time of about 1 day to about 14
days. An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the second embodiment in
this paragraph where R is ethyltrimethylammonium, ETMA.sup.+. An
embodiment of the invention is one, any or all of prior embodiments
in this paragraph up through the second embodiment in this
paragraph where R is diethyldimethylammonium, DEDMA.sup.+. An
embodiment of the invention is one, any or all of prior embodiments
in this paragraph up through the second embodiment in this
paragraph further comprising adding PST-17 seeds to the reaction
mixture.
[0051] A third embodiment of the invention is a hydrocarbon
conversion process comprising contacting a hydrocarbon stream with
a catalyst at hydrocarbon conversion conditions to generate at
least one converted product, wherein the catalyst is selected from
the group consisting of a crystalline microporous PST-17 material,
a modified crystalline microporous PST-17 material and mixtures
thereof, where PST-17 is a crystalline microporous metallophosphate
having a three-dimensional framework of [M.sup.2+O.sub.4/2].sup.2-,
[EO.sub.4/2].sup.- and [PO.sub.4/2].sup.+ tetrahedral units and an
empirical composition in the as synthesized form and anhydrous
basis expressed by an empirical formula of
R.sup.p+.sub.rA.sup.+.sub.mM.sup.2+.sub.xE.sub.yPO.sub.z where R is
at least one quaternary ammonium cation selected from the group
consisting of ethyltrimethylammonium (ETMA.sup.+),
diethyldimethylammonium (DEDMA.sup.+), hexamethonium (HM.sup.2+),
choline [Me.sub.3NCH.sub.2CH.sub.2OH].sup.+,
trimethylpropylammonium, trimethylbutylammonium,
trimethylisopropylammonium, tetramethylammonium (TMA.sup.+),
tetraethylammonium (TEA.sup.+), tetrapropylammonium (TPA.sup.+) and
mixtures thereof, "r" is the mole ratio of R to P and has a value
of about 0.1 to about 1.0, "p" is the weighted average valence of R
and varies from 1 to 2, A is an alkali metal such as Li.sup.t,
Na.sup.+, K.sup.+, Rb.sup.+ and Cs.sup.+ and mixtures thereof, "m"
is the mole ratio of A to P and varies from 0.1 to 1.0, M is a
divalent element selected from the group of Zn, Mg, Co, Mn and
mixtures thereof, "x" is the mole ratio of M to P and varies from
0.2 to about 0.9, E is a trivalent element selected from the group
consisting of aluminum and gallium and mixtures thereof, "y" is the
mole ratio of E to P and varies from 0.1 to about 0.8 and "z" is
the mole ratio of O to P and has a value determined by the equation
z=(m+p r+2 x+3 y+5)/2 and is characterized in that it has the x-ray
diffraction pattern having at least the d-spacings and intensities
set forth in Table A
TABLE-US-00009 TABLE A 2.THETA. d(.ANG.) I/I.sub.0 % 6.90-6.64
12.80-13.31 s-vs 7.76-7.47 11.38-11.83 m-vs 13.34-12.95 6.63-6.83 w
13.68-13.30 6.47-6.65 w-m 14.95-14.63 5.92-6.05 w 15.64-15.32
5.66-5.78 w-m 19.03-18.67 4.66-4.75 w-m 20.45-19.89 4.34-4.46 w-m
21.5-20.98 4.13-4.23 w-m 24.03-23.58 3.70-3.77 w 24.37-23.97
3.65-3.71 w-s 26.75-26.386 3.33-3.375 w-m 27.51-27.04 3.24-3.295
w-m 27.725-27.292 3.215-3.265 w-m 28.59-28.13 3.12-3.17 w-m
28.87-28.45 3.09-3.135 w-m 30.012-29.505 2.975-3.025 w-m
30.38-30.06 2.94-2.97 w-m 30.92-30.38 2.89-2.94 w-m 31.59-31.03
2.83-2.88 w 33.67-33.15 2.66-2.70 w-m 34.20-33.67 2.62-2.66 w-m
35.45-34.88 2.53-2.57 w-m 36.81-36.34 2.44-2.47 w 38.44-37.851
2.34-2.375 w 40.04-39.528 2.25-2.278 w 41.19-40.567 2.19-2.222 w
43.849-43.167 2.063-2.094 w 49.932-49.326 1.825-1.846 w
and the modified crystalline microporous PST-17 consists of a
three-dimensional framework of [M.sup.2+O.sub.4/2].sup.2-,
[EO.sub.4/2].sup.- and [PO.sub.4/2].sup.+ tetrahedral units derived
from PST-17 via the modification processes of calcination, ammonia
calcinations, ion-exchange, steaming, various acid extractions,
ammonium hexafluorosilicate treatment, or any combination thereof.
An embodiment of the invention is one, any or all of prior
embodiments in this paragraph up through the third embodiment in
this paragraph wherein the hydrocarbon conversion process is
selected from the group consisting of cracking, hydrocracking,
alkylation, isomerization, polymerization, reforming,
hydrogenation, dehydrogenation, transalkylation, dealkylation,
hydration, dehydration, hydrotreating, hydrofining,
hydrodenitrogenation, hydrodesulfurization, methanol to olefins,
methanation, syngas shift process, olefin dimerization,
oligomerization, dewaxing, and combinations thereof.
[0052] Without further elaboration, it is believed that using the
preceding description that one skilled in the art can utilize the
present invention to its fullest extent and easily ascertain the
essential characteristics of this invention, without departing from
the spirit and scope thereof, to make various changes and
modifications of the invention and to adapt it to various usages
and conditions. The preceding preferred specific embodiments are,
therefore, to be construed as merely illustrative, and not limiting
the remainder of the disclosure in any way whatsoever, and that it
is intended to cover various modifications and equivalent
arrangements included within the scope of the appended claims.
[0053] In the foregoing, all temperatures are set forth in degrees
Celsius and, all parts and percentages are by weight, unless
otherwise indicated.
* * * * *
References